CN114127150A

CN114127150A - Allophanate-based dispersants

Info

Publication number: CN114127150A
Application number: CN202080051726.1A
Authority: CN
Inventors: A·格南特; 寇会光; S·翁克林; C·奥施拉; J·H·维伦巴切尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2019-07-18
Filing date: 2020-07-17
Publication date: 2022-03-01
Also published as: WO2021009351A1; US20220275146A1; EP3999570A1; US11897995B2

Abstract

The invention relates to a copolymer produced by reacting at least one isocyanate containing at least one allophanate group and at least one reactive double bondEster (A) is reacted with at least one isocyanate-reactive component (B) to form an intermediate product (C) and the intermediate product (C) is reacted with at least one reactive double bond-reactive component (D) to give the copolymer which can be used as a dispersant. The at least one isocyanate-reactive component (B) is selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetherols (B2), C₆‑C₃₀Monofunctional alcohols (B3) and monofunctional polyesterols (B4).

Description

Allophanate-based dispersants

Technical Field

The invention relates to a copolymer which can be used as a dispersant by reacting at least one isocyanate (A) containing at least one allophanate group and at least one reactive double bond with at least one isocyanate-reactive component (B) to form an intermediate product (C) and reacting the intermediate product (C) with at least one reactive double bond-reactive component (D).

Background

Dispersions containing solid dispersible particles, such as organic or inorganic pigments and fillers, and polymeric additives, i.e. dispersants, are used in an almost unlimited number of different technical applications, for example as coatings, for printing inks, for coloring plastics, including fibers, glass or ceramic products, for formulations in cosmetics or for the preparation of paint systems, especially automotive, industrial and decorative paints.

The function of polymeric dispersants in such dispersions is very diverse. They are mainly used as stabilizers for solid particulate materials, i.e. the dispersants separate the particles of the solid particulate material and thus prevent them from agglomerating or clumping and settling out of the liquid phase. They may also be used as solubilizers in a given carrier liquid, for example water or an organic solvent. The polymer additives may also improve the gloss or rheology of the dispersion. Depending on the type and polarity of the dispersant, e.g. water, organic solvents or mixtures thereof, polymers with variable structure are selected. In view of current and future ecological requirements, the use of aqueous pigment dispersions and the use of organic solvent-based dispersions having a high solids content are particularly preferred.

In view of the almost limitless range of different technical applications, there is still an increasing demand for dispersants with improved pigment affinity and rheological properties, expressed by the viscosity of the millbase at a given shear rate, and improved surface coating gloss.

WO 1992/13911 relates to acetoacetanilide functionalized polyalkylene glycols prepared by reacting polyalkylene glycol mono-, di-or triamines with isatoic anhydride and subsequent acetoacetylation of the resulting aminobenzamide.

WO 2000/40630 discloses pigment dispersions containing block copolymers prepared by the ATRP (atom transfer radical polymerization) process of ethylenically unsaturated monomers as dispersants. The block copolymer is composed of defined hydrophobic and hydrophilic polymer blocks.

WO 2003/046029 discloses block copolymers as dispersants which are similar to those of WO 2000/40630 but are subsequently neutralized with specific salt-forming compounds.

WO 2008/107326 and the documents cited therein relate to polyalkylene imine graft polymers of the acrylate, polyether or polyester type, which can be used as pigment dispersants.

Polymers having anthranilate or anthranilamide pendant groups that can be attached to the polymer backbone or polymer terminus either directly or via a divalent spacer have been described several times as crosslinkers or chain extenders for polyurethanes or epoxides, such as the following patent documents:

anthranilate-functionalized polyalkyleneoxides are known, for example, from US 4,180,644, US 4,191,706, US 4,191,835, US 4,247,677, US 4,260,729 and US 2003/212291. The anthranilate-functionalized polyalkylene oxides are useful as crosslinkers for polyurethane or epoxy coatings.

Anthranilate-functionalized polyesters are known, for example, from EP 21569. They are used as chain extenders in the production of polyureas and polyurea-urethanes.

Anthranilate-functionalized polycarbonates are known, for example, from US 5,231,149.

They are used to produce graft or block copolymers having improved impact and solvent resistance.

There is a continuing need to develop dispersants that function as dispersants in coating compositions while having beneficial properties, such as excellent pigment affinity, improved rheology, and improved surface coating gloss.

It is therefore an object of the present invention to provide dispersants which, while being used in coating compositions, have beneficial properties, such as excellent pigment affinity, improved rheology and improved surface coating gloss.

Summary of The Invention

Surprisingly, it has been found that a copolymer obtained by reacting at least one isocyanate (a) comprising at least one allophanate group and at least one reactive double bond with at least one isocyanate-reactive component (B) to form an intermediate product (C) and reacting the intermediate product (C) with at least one reactive double bond-reactive component (D) exhibits advantageous properties when used in coating compositions, such as excellent pigment affinity, improved rheology, improved surface coating gloss, mild (justness) and undertone.

Accordingly, the present invention relates in a first aspect to a copolymer obtainable as follows:

a. reacting at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) to form an intermediate product (C); and

b. reacting the intermediate product (C) obtained in step a. with at least one reactive double bond reactive component (D) to obtain the copolymer;

wherein the at least one isocyanate-reactive component (B) is selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetheralcohols (B2), C₆-C₃₀Monofunctional alcohols (B3) and monofunctional polyesterols (B4).

The present invention relates in a second aspect to a process for preparing a copolymer, wherein the process comprises the steps of:

i) mixing at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) to obtain a mixture;

ii) heating the mixture obtained in step a. to the desired temperature to obtain intermediate product (C);

iii) mixing the intermediate product (C) obtained in step b. with at least one reactive double bond reactive component (D) to obtain a mixture; and

iv) heating the mixture obtained in step c to the desired temperature to obtain the copolymer;

The present invention relates in a third aspect to a liquid composition in the form of a dispersion comprising a copolymer as described herein and a particulate solid material selected from pigments and fillers and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent.

The present invention relates in a fourth aspect to the use of the copolymers described herein and their salts as dispersants for particulate solid materials selected from pigments and fillers.

Detailed Description

Before the present compositions and formulations are described, it is to be understood that this invention is not limited to the particular compositions and formulations described, as such compositions and formulations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

If a group is defined below as comprising at least a certain number of embodiments, this is also intended to include groups preferably consisting of only these embodiments. Furthermore, the terms "first," "second," "third" or "a," "b," "c," and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. Where the terms 'first', 'second', 'third' or '(a)', '(B)' and '(C)' or '(a)', '(B)', '(C)', '(d)', 'i', 'ii', etc. relate to steps of a method or use or analysis, there is no time or time interval coherence between the steps, i.e. the steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between the steps, unless otherwise indicated in the application as context.

Furthermore, the ranges defined throughout the specification are inclusive, i.e., a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalent in accordance with applicable law.

In the following paragraphs, the different aspects of the invention are defined in more detail. Aspects so defined may be combined with any one or more other aspects unless clearly indicated to the contrary. In particular, any feature shown as being preferred or advantageous may be combined with any other feature or features shown as being preferred or advantageous.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may.

Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art from this disclosure. Furthermore, although some embodiments described herein include some, but not other, features included in other embodiments, combinations of features of different embodiments are intended to be within the scope of the invention and form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

In one embodiment, the present invention relates to a copolymer obtained by:

a. reacting at least one isocyanate (A) comprising at least one allophanate group and at least one reactive double bond with at least one compound selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetheralcohols (B2), C₆-C₃₀The isocyanate-reactive components (B) of the monofunctional alcohol (B3) and of the monofunctional polyesterol (B4) react to form an intermediate product (C); and

more preferably a copolymer obtained as follows:

a. reacting at least one isocyanate (A) comprising at least one allophanate group and at least one reactive double bond with at least one compound selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetheralcohols (B2) and C₆-C₃₀Reacting the isocyanate-reactive component (B) of the monofunctional alcohol (B3) to form an intermediate product (C); and

even more preferably a copolymer obtained as follows:

a. reacting at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) selected from monofunctional polyetheramines (B1) and monofunctional polyetheralcohols (B2) to form an intermediate product (C); and

b. reacting the intermediate product (C) obtained in step a. with at least one reactive double bond reactive component (D) to obtain the copolymer; and

most preferred is a copolymer obtained as follows:

a. reacting at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one monofunctional polyetheramine (B1) to form an intermediate product (C); and

wherein the at least one reactive double bond reactive component (D) is selected from primary and secondary amines.

Isocyanate (A)

In a preferred embodiment, the isocyanate (A) is an aliphatic or cycloaliphatic or aromatic polyisocyanate of formula (A):

wherein x is an integer from 1 to 10;

R_ais a divalent aliphatic radical C₂-C₂₀Hydrocarbon units or alicyclic C₅-C₂₀Hydrocarbon units or aromatic C₅-C₂₀A hydrocarbon unit;

z is selected from-O-, -NR₅-and-S-;

R₁and R₂Independently of one another, selected from H, substituted or unsubstituted, linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

g is selected from- (CH)₂)_k-O-、-(CH₂-CH₂-O)_m-、-(-CH(R³)-CH(R⁴)-O-)_n-、-CH₂-CH(OH)-CH₂-O-C(＝O)-C(CH₃)＝CH₂and-CH₂-CH(O-)-CH₂-O-C(＝O)-CH＝CH₂；

Wherein k, m and n are each independently an integer in the range from ≥ 1 to ≤ 20,

R₃and R₄Independently of one another, selected from H, methyl, ethyl, propyl, isopropylN-butyl, isobutyl and tert-butyl,

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

more preferably, the isocyanate (A) is an aliphatic or cycloaliphatic or aromatic polyisocyanate of formula (A):

wherein x is an integer from 1 to 10;

z is selected from-O-, -NR₅-and-S-;

R₁and R₂Independently of one another, selected from H, substituted or unsubstituted, linear or branched C₁-C₂₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₂₀Alkenyl and substituted or unsubstituted phenyl;

R₃and R₄Independently of one another, from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl,

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₂₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₂₀Alkenyl and substituted or unsubstitutedPhenyl of (a);

even more preferably, the isocyanate (A) is an aliphatic or cycloaliphatic or aromatic polyisocyanate of formula (A):

wherein x is an integer from 1 to 5;

z is selected from-O-and-NR₅-；

R₁And R₂Independently of one another, selected from H, substituted or unsubstituted, linear or branched C₁-C₁₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₁₀Alkenyl and substituted or unsubstituted phenyl;

R₃and R₄Independently of one another, selected from the group consisting of H and methyl,

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₁₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₁₀Alkenyl and substituted or unsubstituted phenyl;

most preferably, the isocyanate (A) is an aliphatic or cycloaliphatic or aromatic polyisocyanate of formula (A):

wherein x is an integer from 2 to 5;

R_ais a divalent aliphatic radical C₂-C₂₀Hydrocarbon units or alicyclic C₅-C₂₀Hydrocarbon units or aromatic C₅-C₂₀A hydrocarbon unit; z is selected from-O-and-NR₅-；

R₁And R₂Selected from H, substituted or unsubstituted, linear or branched C₁-C₃Alkyl and substituted or unsubstituted linear or branched C₂-C₃An alkenyl group;

g is selected from- (CH)₂)_k-O-、-(CH₂-CH₂-O)_m-and- (-CH (R)³)-CH(R⁴)-O-)_n-；

R₃and R₄Independently of one another, from H and methyl, and

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₃Alkyl and substituted or unsubstituted linear or branched C₂-C₃An alkenyl group; and

isocyanates (A) are in particular aliphatic or cycloaliphatic or aromatic polyisocyanates of the formula (A):

wherein x is an integer from 2 to 5;

z is selected from-O-and-NR₅-；

R₁And R₂Is H;

g is selected from- (CH)₂-CH₂-O)_m-and- (-CH (R)³)-CH(R⁴)-O-)_n-；

R₃and R₄Independently of one another, from H and methyl, and

R₅is H.

In a preferred embodiment, the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of the formula (a 2):

wherein Z is selected from-O-, -NR₅-and-S-;

g is selected from- (CH)₂)_k-OH、-(CH₂-CH₂-O)_mH、-(-CH(R³)-CH(R⁴)-O-)_n-H、-CH₂-CH(OH)-CH₂-O-C(＝O)-C(CH₃)＝CH₂and-CH₂-CH(OH)-CH₂-O-C(＝O)-CH＝CH₂；

more preferably the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of formula (a 2):

wherein Z is selected from-O-, -NR₅-and-S-;

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₂₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₂₀Alkenyl and substituted or unsubstituted phenyl;

even more preferably the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of formula (a 2):

wherein Z is selected from the group consisting of-O-and-NR₅-；

R₁And R₂Independently of one another, from H, substituted or unsubstituted threadsLinear or branched C₁-C₁₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₁₀Alkenyl and substituted or unsubstituted phenyl;

g is selected from- (CH)₂-CH₂-O)_mH and- (-CH (R)³)-CH(R⁴)-O-)_n-H；

most preferably, the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of formula (a 2):

wherein Z is selected from the group consisting of-O-and-NR₅-；

g is selected from- (CH)₂-CH₂-O)_mH and- (-CH (R)³)-CH(R⁴)-O-)_n-H，

Wherein m and n are each independently an integer in the range from ≥ 1 to ≤ 10,

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₃Alkyl, substituted or unsubstituted linearOr branched C₂-C₆Alkenyl and substituted or unsubstituted phenyl; and the at least one isocyanate (A) comprising at least one allophanate group and at least one activated double bond is obtained in particular by reacting at least one polyisocyanate (A1) with at least one compound of the formula (A2):

wherein Z is selected from the group consisting of-O-and-NR₅-；

R₁And R₂Is H;

g is selected from- (CH)₂-CH₂-O)_mH and- (-CH (R)³)-CH(R⁴)-O-)_n-H；

R₃and R₄Independently of one another, from H and methyl, and

R₅is H.

In another preferred embodiment, the polyisocyanate (A1) is C₂-C₂₀Aliphatic polyisocyanates or C₅-C₂₀Cycloaliphatic polyisocyanate or C₅-C₂₀An aromatic polyisocyanate.

In another preferred embodiment, the polyisocyanate (a1) is a diisocyanate.

In another preferred embodiment, the diisocyanate (A1) is C₂-C₂₀Aliphatic diisocyanates or C₅-C₂₀Cycloaliphatic diisocyanate or C₅-C₂₀An aromatic diisocyanate.

In another preferred embodiment, the aliphatic and cycloaliphatic diisocyanates are selected from the group consisting of tetramethylene diisocyanate, isophorone diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (1, 6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates, such as 1,4-, 1, 3-or 1, 2-diisocyanatocyclohexane, 4,4 '-or 2,4' -bis (isocyanatocyclohexyl) methane, 1-isocyanato-3, 3, 5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane and 2, 4-or 2, 6-diisocyanato-1-methylcyclohexane.

In another preferred embodiment, the aromatic diisocyanate is selected from the group consisting of 2, 4-or 2, 6-toluene diisocyanate, m-or p-xylylene diisocyanate, 2,4' -or 4,4' -diisocyanatodiphenylmethane, 1, 3-or 1, 4-phenylene diisocyanate, 1-chloro-2, 4-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, biphenyl-4, 4' -diisocyanate, 4,4' -diisocyanato-3, 3' -dimethylbiphenyl, 3-methyldiphenylmethane-4, 4' -diisocyanate and diphenylether-4, 4' -diisocyanate.

In a further preferred embodiment, the isocyanate groups of the polyisocyanate (a1) may also be present in blocked form. Examples of suitable NCO-group blocking agents are oximes, phenols, imidazoles, pyrazoles, pyrazolones, diketopiperazines, caprolactams, malonates or compounds as described in the publications Z.W.Wicks, prog.org.coat.3(1975)73-99 and prog.org.coat.9(1981)3-28 and also Houben-Weyl, Methoden der Organischen Chemie, volume XIV/2, page 61 and subsequent pages, Georg Thieme Verlag, Stuttgart 1963.

In another preferred embodiment, the at least one polyisocyanate (a1) is preferably used in the form of a mixture comprising:

I) 1-100% by weight of a polyisocyanate as defined above;

II)0 to 99% by weight, in addition to one or more isocyanate groups, of another compound comprising a group selected from the series consisting of urethane, urea, biuret, allophanate, carbodiimide, uretonimine, uretdione and isocyanurate groups:

IIa) in addition to the polyisocyanates, the isocyanates which may be present in the above-mentioned mixtures are aliphatic and aromatic diisocyanates and in particular polyisocyanates having a higher functionality selected from the group consisting of the following. Polyisocyanates containing isocyanurate groups and derived from aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanates are preferred. The isocyanatoisocyanurates generally have an NCO content of from 10 to 30% by weight, in particular from 15 to 25% by weight, and an average NCO functionality of from 2.6 to 4.5. Particularly suitable are the isocyanurates of the formula (A1a) or oligomeric forms derived therefrom:

wherein R is_aAs defined for the compounds of formula (A).

IIb) the diisocyanates containing uretdione groups and having isocyanate groups bound to aromatic, aliphatic and/or cycloaliphatic structures are preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Polydiazetidinone diisocyanates are the dimerization products of diisocyanates.

IIc) polyisocyanates containing biuret groups and having isocyanate groups attached to aliphatic structures, in particular tris (6-isocyanatohexyl) biuret or its mixtures with its higher homologues. These biuret polyisocyanates generally have NCO contents of from 10 to 30% by weight, in particular from 18 to 25% by weight, and an average NCO functionality of from 2.8 to 4.5.

IId) polyisocyanates containing urethane and/or allophanate groups and having isocyanate groups attached to aliphatic or cycloaliphatic structures, which are free of radically polymerizable C-C double bonds, the C-C double bonds being in activated form either as a result of the carbonyl groups attached directly thereto or as a result of the oxygen atoms in the ether functions. Such compounds can be prepared, for example, by reacting an excess of hexamethylene diisocyanate or isophorone diisocyanate with a mono-or polyhydroxy C₁-C₂₀Monohydric alcohols, polyhydric alcohols such as ethylene glycol, trimethylolpropane, glycerol or mixtures thereof. These contain urethanes andthe allophanate group-containing polyisocyanates generally have an NCO content of from 12 to 25% by weight and an average NCO functionality of from 2.5 to 4.5.

IIe) a polyisocyanate derived from one molecule of alcohol and one molecule of polyisocyanate used in the preparation of the compound of formula (A1).

IIf) contains

The polyisocyanates of the diazinetrione group are preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such compositions contain

The diazinetrione-group polyisocyanates can be prepared from diisocyanates and carbon dioxide.

IIg) carbodiimide or uretonimine modified polyisocyanates.

In another preferred embodiment, the at least one compound of the formula (a2) is an ester of an α, β -unsaturated carboxylic acid with a polyol having at least two hydroxyl groups or an amide of an ethylenically unsaturated carboxylic acid with an amino alcohol.

In a further preferred embodiment, the at least one compound of the formula (A2) is derived from acrylic acid, methacrylic acid, crotonic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinylacetic acid and also polyols preferably having from 2 to 20 carbon atoms and at least 2 hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 4-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, trimethylolpropane, mixtures of these compounds, and mixtures of these compounds, Di-trimethylolpropane, erythritol and sorbitol, and also the vinyl ethers of the abovementioned polyols, provided that they still have a free OH group.

In another preferred embodiment, the compounds of formula (A2) are also derived from α, β -unsaturated carboxylic acids and amino alcohols such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol and 2- (2-aminoethoxy) ethanol.

In another preferred embodiment, the compound of formula (A2) is selected from the group consisting of 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1, 4-butanediol monoacrylate, neopentyl glycol monoacrylate, glycerol mono-and diacrylate, trimethylolpropane mono-and diacrylate, pentaerythritol di-and triacrylate, 2-thioethyl acrylate, thiopropyl acrylate, 1, 4-butanedithiol monoacrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, and mixtures thereof, 1, 4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono-and di (meth) acrylate, trimethylolpropane mono-and di (meth) acrylate, pentaerythritol di-and tri (meth) acrylate, 2-thioethyl (meth) acrylate, thiopropyl (meth) acrylate and 1, 4-butanedithiol mono (meth) acrylate. More preferably, the at least one compound of formula (A2) is selected from the group consisting of 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1, 4-butanediol monoacrylate, neopentyl glycol monoacrylate, glycerol mono-and diacrylate, trimethylolpropane mono-and diacrylate, pentaerythritol di-and triacrylate, 2-thioethyl acrylate, thiopropyl acrylate, 1, 4-butanedithiol monoacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 1, 4-butanediol monoacrylate and 3-acryloyloxy-2-hydroxypropyl methacrylate.

In another preferred embodiment, the compound of formula (A2) is an amide of an ethylenically unsaturated carboxylic acid with an amino alcohol, selected from hydroxyalkyl (meth) acrylamides such as N-methylolacrylamide, N-methylolmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide and 5-hydroxy-3-oxopentyl (meth) acrylamide, N-hydroxyalkylcrotomides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.

In another preferred embodiment, the at least one isocyanate (A) comprising at least one allophanate group and at least one activated double bond is prepared by reacting a polyisocyanate (A1) and an alcohol (A2) at a reaction temperature in the range from ≥ 0 ℃ to ≤ 280 ℃, preferably from ≥ 20 ℃ to ≤ 250 ℃ in the presence of a catalyst which promotes allophanate formation.

In another preferred embodiment, the catalyst promoting allophanate formation is an organozinc compound selected from zinc acetylacetonate and zinc 2-ethylhexanoate, or a tetraalkylammonium compound, such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide or such as N, N, N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, or a zirconyl compound of formula (Z1) or (Z2):

wherein R is_yAnd R_zIndependently of one another from alkyl carbons

Oxy, alkoxy, alkyl, halogen radicals and the hydrogen residue of mineral acids;

wherein R is_s、R_t、R_uAnd R_wIndependently of one another, from the group consisting of alkyl, alkenyl and alkynyl.

In another preferred embodiment, the molar ratio of the polyisocyanate (A1) to the alcohol (A2) used is generally in the range from 1.0:1.0 to 30:1.0, preferably from 1.5:1.0 to 20: 1.0.

In a further preferred embodiment, from 0.001 to 2.0% by weight, in particular from 0.005 to 1.0% by weight, of a polymerization inhibitor is preferably added to the reaction in order to stabilize the free-radically polymerizable compound, i.e. the at least one isocyanate (A) comprising at least one allophanate group and at least one reactive double bond. These compounds are conventional compounds suitable for preventing free-radical polymerization, examples being hydroquinones or hydroquinone monoalkyl ethers, 2, 6-di-tert-butylphenols, such as 2, 6-di-tert-butylcresol, nitrosamines, phenothiazines or phosphites.

In another preferred embodiment, the isocyanates (A) have an active double bond in the range from ≥ 1.0 to ≤ 10.0, more preferably the isocyanates (A) have an active double bond in the range from ≥ 1.0 to ≤ 8.0, even more preferably the isocyanates (A) have an active double bond in the range from ≥ 1.0 to ≤ 6.0, most preferably the isocyanates (A) have an active double bond in the range from ≥ 1.0 to ≤ 5.0, in particular the isocyanates (A) have 1,2 or 3 active double bonds.

In another preferred embodiment, the at least one activated double bond is a double bond conjugated with at least one carbonyl group.

In a further preferred embodiment, the at least one isocyanate (a) comprising at least one allophanate group and at least one reactive double bond contains 1,2,3, 4, 5, 6, 7, 8, 9 or 10 NCO groups, more preferably 1,2,3, 4, 5, 6, 7 or 8 NCO groups, even more preferably 1,2,3, 4, 5 or 6 NCO groups, most preferably 2,3 or 4 NCO groups, in particular 2 or 3 NCO groups.

In a further preferred embodiment, the isocyanate groups of the at least one isocyanate (a) may also be present in blocked form. Examples of suitable NCO-group blocking agents are oximes, phenols, imidazoles, pyrazoles, pyrazolones, diketopiperazines, caprolactams, malonates or compounds as described in the publications Z.W.Wicks, prog.org.coat.3(1975)73-99 and prog.org.coat.9(1981)3-28 and also Houben-Weyl, Methoden der Organischen Chemie, volume XIV/2, page 61 and subsequent pages, Georg Thieme Verlag, Stuttgart 1963.

Isocyanate reactive component (B)

In another preferred embodiment, the at least one isocyanate-reactive component (B) is selected from monofunctional polyetheramines (B1), monofunctional polyetherols (B2), monofunctional alcohols having at least 10 carbon atoms (B3) and monofunctional polyesterols (B4).

In a preferred embodiment, the monofunctional polyetheramine (B1) is a primary or secondary amine of the formula (B1):

wherein Y is selected from H, substituted or unsubstituted linear or branched C₁-C₃₀Alkyl and G- (O (CH)₂)_sCH₂)_o-(CH₂-CH(Q))_p-；

o and p are each independently an integer in the range of 0 to 2000;

s is an integer ranging from more than or equal to 1 to less than or equal to 10;

wherein o + p is an integer ranging from 1 to 4000; and

q and G are independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl;

more preferably Y is selected from H, substituted or unsubstituted linear or branched C₁-C₂₀Alkyl and G- (O (CH)₂)_sCH₂)_o-(CH₂-CH(Q))_p-；

o and p are each independently an integer in the range of 0 to 1000;

s is an integer ranging from more than or equal to 1 to less than or equal to 6;

wherein o + p is an integer in the range of not less than 1 and not more than 2000; and

q and G are independently selected from methyl, ethyl, propyl and isopropyl;

most preferably Y is selected from H, substituted or unsubstituted linear or branched C₁-C₁₀Alkyl and G- (O (CH)₂)_sCH₂)_o-(CH₂-CH(Q))_p-；

o and p are each independently an integer in the range of 0 to 500;

s is an integer ranging from more than or equal to 1 to less than or equal to 4;

wherein o + p is an integer in the range of not less than 1 and not more than 1000; and

q and G are independently selected from methyl and ethyl;

y is chosen in particular from H and substituted or unsubstituted, linear or branched C₁-C₄An alkyl group, a carboxyl group,

o and p are each independently an integer in the range of 0 to 100;

s is an integer ranging from more than or equal to 1 to less than or equal to 2;

wherein o + p is an integer in the range of not less than 1 and not more than 200; and

q and G are methyl.

In another preferred embodiment, the monofunctional polyetheramine (B1) is a primary amine of the formula (B1 a):

wherein p is an integer in the range of 0 or more to 2000 or less, and

q is selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl, and

g is a substituted or unsubstituted linear or branched C₁-C₃₀An alkyl group;

more preferably p is an integer in the range of ≥ 1 to ≤ 500,

q is selected from H and methyl, and

even more preferably p is an integer in the range from ≥ 1 to ≤ 100,

q is selected from H and methyl, and

most preferably p is an integer in the range of ≥ 1 to ≤ 50,

q is selected from H and methyl, and

g is a substituted or unsubstituted linear or branched C₁-C₃₀An alkyl group; and

p is in particular an integer in the range from ≥ 3 to ≤ 20,

q is selected from H and methyl, and

g is a substituted or unsubstituted linear or branched C₁-C₃₀An alkyl group.

In another preferred embodiment, the monofunctional polyetheramine (B1a) is a primary amine of formula (B1aa) or (B1 ab):

wherein p is an integer in the range of 0 or more to 2000 or less, and

q is selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl;

wherein o and p are in each case, independently of one another, integers in the range from ≥ 0 to ≤ 2000,

wherein o + p is an integer in the range of not less than 1 and not more than 4000, and

more preferably, the monofunctional polyetheramine (B1) is a primary amine of formula (B1aa) or (B1 ab):

wherein p is an integer in the range of not less than 1 and not more than 500, and

q is selected from the group consisting of H and methyl,

wherein o and p are in each case, independently of one another, integers in the range from ≥ 0 to ≤ 500,

wherein o + p is an integer in the range of not less than 1 and not more than 1000, and

q is selected from H and methyl;

most preferably, the monofunctional polyetheramine (B1) is a primary amine of formula (B1aa) or (B1 ab):

wherein p is an integer in the range of from ≥ 1 to ≤ 100, and

q is selected from the group consisting of H and methyl,

wherein o and p are in each case, independently of one another, integers in the range from ≥ 0 to ≤ 100,

wherein o + p is an integer in the range of not less than 1 and not more than 200, and

q is selected from H and methyl.

In a preferred embodiment, the monofunctional polyetheramine (B1) is a primary amine of formula (B1aa) or (B1 ab):

wherein p is an integer in the range of 2 to 50, and

q is selected from the group consisting of H and methyl,

wherein o and p are in each case, independently of one another, integers in the range from ≥ 2 to ≤ 50,

wherein o + p is an integer in the range of 2 to 100, and

q is selected from H and methyl; and

wherein p is an integer in the range of 3 to 20, and

q is a hydrogen atom (H) or a hydrogen atom (H),

wherein o and p are in each case, independently of one another, integers in the range from ≥ 3 to ≤ 20,

wherein o + p is an integer in the range of not less than 3 and not more than 40; and

q is methyl.

In another preferred embodiment, the compound of formula (B1) is selected from CH₃-(OCH₂CH₂)₃₂-(OCH₂CH(CH₃))₁₀-NH₂、CH₃-(OCH₂CH₂)₁-(OCH₂CH(CH₃))₉-NH₂、CH₃-(OCH₂CH₂)₁₉-(OCH₂CH(CH₃))₃-NH₂、CH₃-(OCH₂CH₂)₆-(OCH₂CH(CH₃))₂₉-NH₂、CH₃-(OCH₂CH₂)_18.6-(OCH₂CH(CH₃))_1.6-OCH₂CH(CH₃)-NH₂And CH₃-(OCH₂CH₂)₃₁-(OCH₂CH(CH₃))₁₀-NH₂。

In another preferred embodiment, the monofunctional polyetheramine (B1) has a weight-average molecular weight, determined by GPC, in the range from ≥ 120g/mol to ≤ 10000 g/mol. More preferably, the monofunctional polyetheramine (B1) has a weight-average molecular weight, determined by GPC, in the range from ≥ 300g/mol to ≤ 8000 g/mol. Even more preferably, the monofunctional polyetheramine (B1) has a weight-average molecular weight, determined by GPC, in the range from ≥ 200g/mol to ≤ 5000 g/mol. Most preferably, the monofunctional polyetheramine (B1) has a weight average molecular weight, as determined by GPC, in the range from ≥ 300g/mol to ≤ 4000g/mol, and particularly preferably, the monofunctional polyetheramine (B1) has a weight average molecular weight, as determined by GPC, in the range from ≥ 500g/mol to ≤ 4000 g/mol.

In another preferred embodiment, the isocyanate-reactive component (B) is a monofunctional polyether alcohol (B2) of the formula:

wherein o and p are each independently an integer in the range from ≥ 0 to ≤ 2000,

s is an integer of more than or equal to 1 and less than or equal to 10,

wherein o + p is an integer of 1 to 4000 inclusive,

R₆selected from substituted or unsubstituted linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl; and

q is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and substituted or unsubstituted phenyl;

more preferably, the isocyanate-reactive component (B) is a monofunctional polyether alcohol (B2) of the formula:

wherein o and p are each independently an integer in the range from ≥ 0 to ≤ 500,

s is an integer ranging from 1 to 10 or less, wherein o + p is an integer ranging from 1 to 1000 or less,

wherein o and p are each independently an integer in the range from ≥ 0 to ≤ 100,

s is an integer of more than or equal to 1 and less than or equal to 10,

wherein o + p is an integer in the range of not less than 1 and not more than 200,

R₆selected from substituted or unsubstituted linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl, and

q is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and substituted or unsubstituted phenyl; and

particularly preferred isocyanate-reactive component (B) is a monofunctional polyether alcohol (B2) of the formula:

s is an integer of more than or equal to 1 and less than or equal to 10,

q is methyl.

In another preferred embodiment, the at least one isocyanate-reactive component (B) is a monofunctional polyether alcohol (B2) selected from the group consisting of formula (B2a) and formula (B2B).

In another preferred embodiment, the formula (B2a) is:

wherein

p is an integer ranging from more than or equal to 1 to less than or equal to 2000;

q is selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl; and

R₆is substituted or unsubstituted, linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

more preferably, p is an integer in the range of ≥ 1 to ≤ 500;

q is selected from H and methyl; and

most preferably, p is an integer in the range of from ≥ 1 to ≤ 100;

q is selected from H and methyl; and

R₆is substituted or unsubstituted, linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl; and

p is in particular an integer from ≥ 1 to ≤ 50;

q is selected from H and methyl; and

R₆is substituted or unsubstituted, linear or branched C₁-C₃₀An alkyl group.

In another preferred embodiment, the formula (B2B) is:

wherein

p and o are each independently an integer in the range from 0 to 2000,

o + p is an integer of 1 to 4000 inclusive; q is selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl; and

R₆selected from substituted or unsubstituted linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

more preferably, p and o are, independently of each other, an integer in the range from ≥ 0 to ≤ 500, and o + p is an integer in the range from ≥ 1 to 1000; q is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and substituted or unsubstituted phenyl; and R₆Selected from substituted or unsubstituted linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

most preferably wherein p and o are independently an integer in the range from ≥ 0 to ≤ 100, and o + p is an integer in the range from ≥ 1 to ≤ 200; q is selected from methyl; and R is₆Is substituted or unsubstituted, linear or branched C₁-C₃₀An alkyl group; and

p and o are in particular, independently of one another, integers in the range from ≥ 0 to ≤ 50, o + p being an integer in the range from ≥ 1 to ≤ 100; q is selected from methyl; and R is₆Is substituted or unsubstituted, linear or branched C₁-C₃₀An alkyl group.

In a further preferred embodiment, the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 150g/mol to ≤ 10000 g/mol. More preferably, the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 150g/mol to ≤ 6000 g/mol. Even more preferably, the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 150g/mol to ≤ 5000 g/mol. Most preferably, the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 250g/mol to ≤ 4000 g/mol.

In another preferred embodiment, the at least one isocyanate reactive component (B) is a saturated or unsaturated branched or linear monofunctional alcohol having at least 10 carbon atoms (B3), more preferably the monofunctional alcohol (B3) is a saturated or unsaturated branched or linear monofunctional alcohol having from 10 to 30 carbon atoms, most preferably the monofunctional alcohol (B3) is a saturated or unsaturated branched or linear monofunctional alcohol having from 10 to 24 carbon atoms; it is particularly preferred that the monofunctional alcohol (B3) is a saturated or unsaturated branched or linear monofunctional alcohol having from 10 to 18 carbon atoms.

In another preferred embodiment, the compound of formula (B3) is selected from the group consisting of decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, decan-2-ol, undecan-2-ol, dodecane-2-ol, tridecan-2-ol, tetradecan-2-ol, pentadecan-2-ol, hexadecan-2-ol, heptadecan-2-ol, octadecan-2-ol, nonadecan-2-ol, eicosan-2-ol, heneicosane-2-ol, docosan-2-ol, decan-3-ol, undecan-3-ol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol-2-ol, hexadecanol-3-ol, dodecanol, and mixtures thereof, Dodecane-3-ol, tridecan-3-ol, tetradecan-3-ol, pentadecan-3-ol, hexadecan-3-ol, heptadecane-3-ol, octadecan-3-ol, nonadecane-3-ol, eicosan-3-ol, heneicosan-3-ol, docosane-3-ol, decan-4-ol, undecane-4-ol, dodecane-4-ol, tridecan-4-ol, tetradecan-4-ol, pentadecan-4-ol, hexadecan-4-ol, heptadecane-4-ol, octadecan-4-ol, nonadecane-4-ol, eicosan-4-ol, Heneicosane-4-ol, docosane-4-ol, stearyl alcohol, palmitoleyl alcohol, oleyl alcohol, and erucyl alcohol.

In another preferred embodiment, the at least one isocyanate-reactive component (B) is a monofunctional polyesterol (B4). The monohydroxy polyesterol may contain at least one- -COO- -group, a polyester or a mixed polyether-polyester. The monohydroxy polyesterol is obtained by polymerizing a lactone such as propiolactone, valerolactone, caprolactone or substituted derivatives thereof using a monohydroxy starting component. The starting materials used may be those having preferably from 4 to 40, more preferably from 10 to 40,even more preferably from 10 to 30 carbon atoms. The monoalcohols are selected from, but not limited to, n-butanol, saturated and unsaturated alcohols such as propargyl alcohol, oleyl alcohol, linoleyl alcohol, oxo alcohols, cyclohexanol, phenylethanol or neopentyl alcohol or fluoroalcohols and also substituted and unsubstituted phenols can be converted into polyoxyalkylene monoalkyl-, aryl-, aralkyl-or cycloalkyl ethers by known methods of alkoxylation with ethylene oxide and/or propylene oxide, and these monohydroxy polyethers can be used as starting components for the lactone polymerization to obtain monohydroxy polyesterols (B4). In another preferred embodiment, propiolactone, valerolactone and caprolactone are reacted with monohydroxy C₁₀-C₃₀The alcohol is polymerized to give the monohydroxy polyesterol (B4).

In another preferred embodiment, the reaction of at least one isocyanate (A) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) to form the intermediate product (C) is carried out at a reaction temperature in the range from ≥ 0 ℃ to ≤ 280 ℃, more preferably ≥ 20 ℃ to ≤ 250 ℃ in the presence or absence of a catalyst and in the presence or absence of a solvent.

In another preferred embodiment, intermediate (C) is prepared in the presence of at least one inert solvent selected from the group consisting of acetone, methyl ethyl ketone, tetrahydrofuran, and bis

C of alkane, dichloromethane, toluene, xylene and acetic acid₁-C₄Alkyl esters such as ethyl acetate, propyl acetate, butyl carbitol acetate, ether solvents such as methyl isobutyl ether, glycol ether acetates, and mineral oils, mineral spirits, natural oils, methyl amyl ketone, ethyl cellosolve, cyclohexane, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and mixtures thereof.

In a further preferred embodiment, the intermediate product (C) obtained in step a. has an NCO content of < 0.2% by weight relative to the total weight of the intermediate product (C). More preferably, the intermediate product (C) obtained in step a. has an NCO content of <0.1 wt. -% relative to the total weight of the intermediate product (C), even more preferably the intermediate product (C) obtained in step a. has an NCO content of <0.05 wt. -% relative to the total weight of the intermediate product (C), most preferably the intermediate product (C) obtained in step a. has an NCO content of <0.01 wt. -% relative to the total weight of the intermediate product (C), especially preferably the intermediate product (C) obtained in step a. has no NCO content.

In another preferred embodiment, the copolymer is obtained by reacting the intermediate product (C) obtained with at least one reactive double bond reactive component (D).

Component (D)

In a preferred embodiment, the at least one active double bond reactive component (D) is a primary or secondary amine. The primary and secondary amines preferably contain a heterocycle selected from the group consisting of imidazole, 1H-1,2, 3-triazole, 4H-1,2, 4-triazole, 1H-tetrazole, piperazine, pyrimidine, morpholine, benzimidazole, pyridine, benzothiazole, imidazolidin-2-one, benzylamine and aniline.

In a preferred embodiment, the at least one reactive double bond reactive component (D) is selected from the group consisting of imidazole, 1H-imidazol-1-amine, (1H-imidazol-1-yl) methylamine, (1H-imidazol-1-yl) ethan-1-amine, 3- (1H-imidazol-1-yl) propan-1-amine, 4- (1H-imidazol-1-yl) butan-1-amine, 5- (1H-imidazol-1-yl) pentan-1-amine, N-ethyl-2- (1H-imidazol-1-yl) ethan-1-amine, (1H-imidazol-1-yl) methanethiol, 2- (1H-imidazol-1-yl) ethan-1-thiol, 3- (1H-imidazol-1-yl) propane-1-thiol, 4- (1H-imidazol-1-yl) butane-1-thiol, (1H-1,2, 3-triazol-1-yl) methylamine, 1H-1,2, 3-triazole, 2- (1H-1,2, 3-triazol-1-yl) ethan-1-amine, 3- (1H-1,2, 3-triazol-1-yl) propan-1-amine, 4- (1H-1,2, 3-triazol-1-yl) butan-1-amine, 5- (1H-1,2, 3-triazol-1-yl) pentan-1-amine, (1H-1,2, 3-triazol-1-yl) methanethiol, 2- (1H-1,2, 3-triazol-1-yl) ethan-1-thiol, 3- (1H-1,2, 3-triazol-1-yl) propan-1-thiol, 4- (1H-1,2, 3-triazol-1-yl) butan-1-thiol, 5- (1H-1,2, 3-triazol-1-yl) pentan-1-thiol, 4H-1,2, 4-triazole, (4H-1,2, 4-triazol-4-yl) methylamine, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-amine, 3- (4H-1,2, 4-triazol-4-yl) propan-1-amine, 4- (4H-1,2, 4-triazol-4-yl) butan-1-amine, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-amine, (4H-1,2, 4-triazol-4-yl) methanethiol, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-thiol, 3- (4H-1,2, 4-triazol-4-yl) propan-1-thiol, 4- (4H-1,2, 4-triazol-4-yl) butan-1-thiol, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-thiol, (1H-tetrazol-1-yl) methylamine, 2- (1H-tetrazol-1-yl) ethan-1-amine, 3- (1H-tetrazol-1-yl) propan-1-amine, 4- (1H-tetrazol-1-yl) butan-1-amine, and mixtures thereof, N-methyl-4- (1H-tetrazol-1-yl) butan-1-amine, 5- (1H-tetrazol-1-yl) pentan-1-amine, (1H-tetrazol-1-yl) methanethiol, 2- (1H-tetrazol-1-yl) ethane-1-thiol, 3- (1H-tetrazol-1-yl) propane-1-thiol, 4- (1H-tetrazol-1-yl) butane-1-thiol, 5- (1H-tetrazol-1-yl) pentane-1-thiol, N-diethyl-1, 4-butanediamine, 1- (2-aminoethyl) piperazine, N-methyl-1- (1H-tetrazol-1-yl) butane-1-thiol, N-diethyl-1, 4-butanediamine, N-methyl-1- (1H-tetrazol-1-yl) pentane-1-thiol, N-methyl-1-methyl-1-thiol, N-ethyl-1-butanediamine, N-methyl-1-thiol, N-tetrazol-1-thiol, N-methyl-1-thiol, N-1-methyl-1-thiol, N-methyl-1-thiol, N-methyl-1-methyl-1-one, N-methyl-2-methyl-2-ethyl-methyl-2-one, N, 2- (1-pyrrolidinyl) ethylamine, 4-amino-2-methoxypyrimidine, 2-dimethylaminoethanol, 1- (2-hydroxyethyl) piperazine, 4- (2-hydroxyethyl) morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N-dimethyl-1, 3-propanediamine, 4- (2-aminoethyl) pyridine, 2-amino-6-methoxybenzothiazole, 4-aminomethylpyridine, N-diallylmelamine, 3-amino-1, 2, 4-triazole, 1- (3-aminopropyl) imidazole, 4- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) imidazole, 3-mercapto-1, 2, 4-triazole, 1- (2-aminoethyl) imidazolidin-2-one, benzylamine, aniline, and branched or linear (C)₂H₅N)_1-500And salts thereof.

In another preferred embodiment, the copolymer can be obtained as follows:

a. reacting an isocyanate (a) (1 molar equivalent) of the formula:

wherein x is a positive integer having an average value of 1 to 5, preferably 1 to 3,

ra is- (CH)₂)₆-, G is-O-, and Z is-CH₂-CH₂-，R₁And R₂Is H;

with a monofunctional primary amine polyetheramine copolymer (B) (1-1.1 molar equivalents, based on the NCO content of the isocyanate (A)) having an EO/PO skeleton with a weight-average molecular weight Mw in the range from 500-3000g/mol to form an intermediate (C); and

b. the intermediate (C) obtained in step a. is reacted with N- (3-aminopropyl) imidazole (D) (0.2-1.0 molar equivalents, based on the double bond in isocyanate (a)) to give the copolymer.

In another preferred embodiment, the copolymer is prepared by a process comprising the steps of:

i) mixing at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) to give a mixture;

more preferably, the copolymer is prepared by a process comprising the steps of:

i) at least one isocyanate (A) comprising at least one allophanate group and at least one reactive double bond is reacted with at least one compound selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetheralcohols (B2), C₆-C₃₀The isocyanate-reactive components (B) of monofunctional alcohol (B3) and monofunctional polyesterol (B4) being mixed to give a mixture;

even more preferably the copolymer is prepared by a process comprising the steps of:

i) at least one isocyanate (A) containing at least one allophanate group and at least one reactive double bond is reacted with at least one isocyanate (A)One selected from the group consisting of monofunctional polyetheramine (B1), monofunctional polyetherol (B2) and C₆-C₃₀Isocyanate-reactive components (B) of monofunctional alcohols (B3) to give a mixture;

most preferably the copolymer is prepared by a process comprising the steps of:

i) mixing at least one isocyanate (A) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) selected from monofunctional polyetheramines (B1) and monofunctional polyetheralcohols (B2) to give a mixture;

iv) heating the mixture obtained in step c to the desired temperature to obtain the copolymer; and particularly preferably the copolymer is prepared by a process comprising the steps of:

i) mixing at least one isocyanate (A) comprising at least one allophanate group and at least one activated double bond with at least one monofunctional polyetheramine (B1) to give a mixture;

In a preferred embodiment, the reaction temperature in step ii) in the presence or absence of a catalyst and in the presence or absence of a solvent to give the intermediate (C) is in the range from ≥ 0 ℃ to ≤ 150 ℃, more preferably ≥ 20 ℃ to ≤ 130 ℃.

In another preferred embodiment, the molar ratio between the at least one isocyanate (a) and the at least one isocyanate-reactive component (B) is in the range of from 1.0:1.0 to 1.0: 5.0; more preferably the molar ratio between the at least one isocyanate (a) and the at least one isocyanate-reactive component (B) is in the range of 1.0:1.0 to 1.0: 3.0; even more preferably the molar ratio between the at least one isocyanate (a) and the at least one isocyanate-reactive component (B) is in the range of 1.0:1.0 to 1.0: 2.0; most preferably the molar ratio between the at least one isocyanate (a) and the at least one isocyanate-reactive component (B) is in the range of 1.0:1.0 to 1.0: 1.5; the molar ratio between the at least one isocyanate (a) and the at least one isocyanate-reactive component (B) is in particular in the range from 1.0:1.0 to 1.0: 1.1.

In a preferred embodiment, the reaction temperature at which the copolymer is obtained in step iv) in the presence or absence of at least one solvent is in the range from ≥ 0 ℃ to ≤ 150 ℃, more preferably ≥ 20 ℃ to ≤ 120 ℃.

In another preferred embodiment, the molar ratio between the intermediate (C) and the at least one reactive double bond reactive component (D) is in the range of 1.0:0.1 to 1.0:2.0, more preferably 1.0:0.2 to 1.0: 1.0.

In another preferred embodiment, the process for preparing the copolymer from step i) to step iv) is carried out in the presence of at least one solvent.

In another preferred embodiment, the at least one solvent is selected from acetone, methyl ethyl ketone, tetrahydrofuran, bis

C of alkane, dichloromethane, toluene, xylene and acetic acid₁-C₄Alkyl estersSuch as ethyl acetate, propyl acetate, butyl carbitol acetate, ether solvents such as methyl isobutyl ether, glycol ether acetates, and inert solvents of mineral oil, mineral spirits, natural oils, methyl amyl ketone, ethyl cellosolve, cyclohexane, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and mixtures thereof.

In another preferred embodiment, the liquid composition is in the form of a dispersion comprising at least one copolymer and a particulate solid material selected from pigments and fillers and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent. The at least one copolymer is as defined above. The pigment is selected from organic or inorganic pigments.

In a preferred embodiment, the present invention relates in particular to a liquid composition in the form of a liquid coating composition comprising a particulate solid material, in particular a pigment or filler, and at least one copolymer as defined above-dispersed in a liquid diluent.

In a preferred embodiment, the present invention also relates to, inter alia, a liquid composition in the form of a liquid ink composition comprising a particulate solid material, in particular a pigment or filler, and at least one copolymer as defined above-dispersed in a liquid diluent.

In a preferred embodiment, suitable solid particulate materials include, but are not limited to, pigments and fillers. The pigment includes an inorganic or organic pigment. Pigments may include color pigments and pearlescent flakes.

In a preferred embodiment, the size of the particulate material is preferably in the micrometer range, for example a weight average particle size in the range of 1 to 2000 μm, especially 2 to 1000 μm or 5 to 500 μm. The weight average particle size can be determined by sieve analysis. The weight average particle diameter can also be measured by a light scattering method.

Examples of suitable organic pigments are selected fromThe following pigments and pearlescent flakes: azo, bisazo, naphthol, benzimidazolone, azo condensation, metal complexes, isoindolinone and isoindoline pigments, quinophthalone pigments, bis

An oxazine pigment and a polycyclic pigment selected from: indigo, thioindigo, quinacridones, phthalocyanines, perylenes, perinones, anthraquinones, e.g. aminoanthraquinones or hydroxyanthraquinones, anthrapyrimidines, indanthrones, flavanthrones, pyranthrones, triphenylo [ cd, jk]Pyrene-5, 10-diones (anthantrinones), isoviolanthrones, diketopyrrolopyrroles and carbazoles such as carbazole violet and the like. Other examples of organic pigments can be found in monographs: W.Herbst, K.Hunger "Industrial ville Organische Pigmente", 2 nd edition, 1995, VCH Verlagsgesellschaft, ISBN: 3-527-.

Examples of suitable inorganic pigments are metal flakes, such as aluminum, aluminum oxide, calcium carbonate, silicon oxide and silicates, iron (III) oxide, chromium (III) oxide, titanium (IV) oxide, zirconium (IV) oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, carbon black or graphite, vanadates, such as bismuth vanadate, chromates, such as lead (IV) chromate and molybdates, such as lead (IV) molybdate, and mixtures, crystal forms or crystal forms thereof, such as rutile, anatase, mica, talc or kaolin.

In a preferred embodiment, suitable fillers are calcium carbonate, silicates, glass fibers, glass beads, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, flours and fibers of other natural products and synthetic fibers.

In a preferred embodiment, the choice of the liquid diluent present in the dispersion depends in a known manner on the field of application. The dispersants of the present invention are particularly useful in dispersions where the diluent is selected from solvents commonly used in coating technology. For aqueous formulations, the diluent comprises water and may further comprise, in addition to water, a water-miscible polar solvent, such as C₁-C₄Alkanols, e.g. methanolAlcohols, ethanol, isopropanol, propanol or n-butanol, glycol ethers such as butyl glycol or methoxypropanediol, polyols, for example glycerol, ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol. For solvent based formulations, less polar solvents such as aliphatic hydrocarbons, esters such as butyl acetate or glycol ethers such as methoxypropylene glycol or glycol ether esters such as methoxypropylene glycol acetate and mixtures thereof are preferably used as liquid diluents.

In a preferred embodiment, the weight ratio of the particulate solid material to the at least one copolymer is in the range from ≥ 100:1 to ≤ 1:50, more preferably from 50:1 to 1:30, even more preferably from 30:1 to 1: 10.

In one embodiment, the liquid composition comprises:

a) from ≥ 1% by weight to ≤ 70% by weight, based on the total weight of the liquid composition, of the at least one solid particulate material selected from pigments and fillers;

b) from ≥ 0.5% by weight to ≤ 50% by weight, based on the total weight of the liquid composition, of the at least one copolymer as defined above; and

c) from ≥ 10% by weight to ≤ 98.5% by weight, based on the total weight of the liquid composition, of the at least one liquid diluent.

In a preferred embodiment, the liquid composition may further comprise a binder and/or one or more conventional additives depending on the intended use. Conventional additives include, for example, plasticizers, lubricants, emulsifiers, humectants, rheological additives, catalysts, flow aids, optical brighteners, flame retardants, preservatives, antistatic agents or blowing agents.

In a preferred embodiment, the liquid dispersion may be in the form of a millbase. The mill-base contains the particulate solid, the copolymer and the liquid diluent and optional additives, but the mill-base is generally free of binder.

In a preferred embodiment, the liquid dispersion may also be in the form of a coating composition. The coating composition contains the particulate solid, the at least one copolymer as defined above and the liquid diluent and additionally, one or more binders, such as film-forming polymers or prepolymers, which form a film when cured. The coating compositions may optionally contain conventional additives used in coating technology, such as plasticizers, lubricants, emulsifiers, rheological additives, catalysts, flow aids, optical brighteners, flame retardants, preservatives, antistatic agents or blowing agents.

In a preferred embodiment, the liquid dispersion may also be in the form of a coating composition. The coating composition contains the particulate solid, the at least one copolymer and the liquid diluent and additionally one or more binders, such as film-forming polymers or prepolymers, which form a film upon curing. The coating compositions may optionally contain conventional additives used in coating technology, such as plasticizers, lubricants, emulsifiers, rheological additives, catalysts, flow aids, optical brighteners, flame retardants, preservatives, antistatic agents or blowing agents.

In a preferred embodiment, the liquid dispersion may also be in the form of an ink, for example a printing ink or an intaglio ink. The ink contains the particulate solid, at least one copolymer as defined above and a liquid diluent and, additionally, one or more binders customary in ink technology, such as film-forming polymers or prepolymers which form films when cured. The coating composition may optionally contain conventional additives such as plasticizers, lubricants, emulsifiers, humectants, rheological additives, humectants, preservatives and antistatic agents.

Suitable binders are those which are customary, such as those described In Ullmann's Encyclopedia of In-duration Chemistry, 5 th edition, volume A18, page 368-. The film-forming binders are generally based on thermoplastic or thermosetting resins, preferably thermosetting resins. Examples thereof are alkyd resins, acrylic resins, polyester resins, phenolic resins, melamine resins, epoxy resins and polyurethane resins and mixtures thereof. Resins curable by radiation or air-drying resins may also be used. The binders may also be derived from polyvinyl alcohol and polyvinyl butyral.

If a cold or hot curable binder is used, it may be advantageous to add a curing catalyst. Suitable catalysts for accelerating the curing of the binder are described, for example, in Ullmann's, volume A18, supra, page 469.

In another preferred embodiment, the coating composition comprises a copolymer as defined above and a crosslinkable resin. Examples of coating compositions containing specific binders are:

paints based on cold-or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if desired with addition of a curing catalyst;

two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking, if desired with addition of melamine resins;

one-component polyurethane paints based on trialkoxycarbonyltriazine crosslinkers and hydroxyl-containing resins, such as acrylate, polyester or polyether resins;

one-component polyurethane paints based on aliphatic or aromatic urethane acrylates or polyurethane acrylates having free amino groups in the urethane structure and melamine resins or polyether resins, if necessary with the use of curing catalysts;

two-component paints based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

two-component paints based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;

two-component paints based on carboxyl-or amino-containing polyacrylates and polyepoxides;

two-component paints based on acrylate resins containing anhydride groups and a polyhydroxy or polyamino component;

two-component paints based on acrylate-containing anhydrides and polyepoxides;

based on (poly)

Two-component paints of oxazolines and anhydride-group-containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

two-component paints based on unsaturated polyacrylates and polymalonates;

thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinked acrylate resins in combination with etherified melamine resins; and

lacquer systems based on siloxane-modified or fluorine-modified acrylate resins.

In another preferred embodiment, the coating composition preferably comprises, per 100% by weight of solid binder, from 0.01 to 100.0% by weight, in particular from 0.05 to 50.0% by weight, especially from 0.1 to 20.0% by weight, of the combined components a) and b), i.e. the particulate solid and the at least one copolymer in the composition.

In another preferred embodiment, the coating composition preferably comprises, per 100% by weight of solid binder, from 0.01 to 100.0% by weight, in particular from 0.05 to 50.0% by weight, in particular from 0.1 to 20.0% by weight, of the combined components a) and b), i.e. the particulate solid and the at least one copolymer.

In a preferred embodiment, the pigment is generally dispersed in the liquid diluent in the presence of the at least one copolymer as defined above. This dispersion can be achieved by using conventional techniques such as high speed mixing, ball milling, sand milling, attritor milling or two or three roll milling. The resulting pigment dispersion may have a pigment/dispersant weight ratio within the above ranges. The resulting dispersion is therefore also referred to as millbase.

In a preferred embodiment, the pigment is generally dispersed in the liquid diluent in the presence of the at least one copolymer. This dispersion can be achieved by using conventional techniques such as high speed mixing, ball milling, sand milling, attritor milling or two or three roll milling. The resulting pigment dispersion may have a pigment/dispersant weight ratio within the above ranges. The resulting dispersion is therefore also referred to as millbase.

In another preferred embodiment, a millbase is generally incorporated into the liquid composition of the binder, for example by mixing, in the process for preparing the coating composition or ink. However, it is also possible to disperse the particulate solid in a solution of the at least one copolymer, to concentrate the resulting mixture by evaporating off the solvent and/or water, preferably to dryness, and optionally to subject the resulting concentrate to a thermal and/or mechanical treatment to prepare a mixture comprising pigment and modified copolymer, which can then be dispersed in a liquid binder formulation. According to this process, the solid formulation of the particulate solid and the at least one copolymer as defined above is easy to disperse and does not require time and energy intensive grinding to be incorporated into, for example, a paint formulation.

In another preferred embodiment, a millbase is generally incorporated into the liquid composition of the binder, for example by mixing, in the process for preparing the coating composition or ink. However, it is also possible to disperse the particulate solid in a solution of the at least one copolymer, to concentrate the resulting mixture by evaporating off the solvent and/or water, preferably to dryness, and optionally to subject the resulting concentrate to a thermal and/or mechanical treatment to prepare a mixture comprising pigment and modified copolymer, which can then be dispersed in a liquid binder formulation. According to the method, the solid formulation of the particulate solid and the at least one copolymer is easy to disperse and does not require time and energy intensive grinding for incorporation into, for example, a paint formulation.

The present invention relates in a further aspect to the use of the at least one copolymer as defined above as a dispersant for particulate solid materials selected from pigments and fillers.

The present invention provides one or more of the following advantages:

1. the invention provides a dispersant prepared as follows:

2. The copolymers exhibit beneficial properties when used in coating compositions, such as excellent pigment affinity, improved rheology, improved surface coating gloss, body and undertone.

Specific embodiments of the invention are described below:

1. a copolymer obtained as follows:

2. The copolymer according to embodiment 1, wherein the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond contains 1,2,3, 4, 5, 6, 7, 8, 9 or 10 NCO groups.

3. The copolymer according to embodiment 1, wherein the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of formula (a 2):

wherein Z is selected from-O-, -NR₅-and-S-;

k. m and n are each independently an integer in the range of 1 to 20;

R₃and R₄Independently of one another, selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and

R₅selected from H, substituted or unsubstituted, linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl.

4. The copolymer according to embodiment 3, wherein the at least one polyisocyanate (A1) is selected from 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 3-or 1, 4-phenylene diisocyanate, triphenylmethane-4, 4',4 "-triisocyanate, polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, 1, 3-cyclobutane diisocyanate, 1, 3-or 1, 4-cyclohexane diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane, 2, 4-or 2, 6-hexahydrotoluene diisocyanate, hexahydro-1, 3-or-1, 4-phenylene diisocyanate and perhydro-2, 4 '-or-4, 4' -dicyclohexylmethane diisocyanate.

5. The copolymer according to embodiment 3, wherein the at least one compound of formula (A2) is selected from the group consisting of hydroxyacrylate (A2a) and hydroxyacrylamide (A2 b).

6. The copolymer according to any of the preceding embodiments, wherein the at least one isocyanate (A) has an activated double bond in the range ≥ 1 to ≤ 10.

7. The copolymer according to any of the preceding embodiments, wherein the at least one activated double bond is a double bond conjugated to at least one carbonyl group.

8. The copolymer according to any of embodiments 1-7, wherein the monofunctional polyetheramine (B1) has the formula (B1):

o and p are each independently an integer in the range of 0 to 2000;

wherein o + p is within the range of more than or equal to 1 and less than or equal to 4000; and

q and G are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

9. The copolymer according to any of embodiments 1 to 8, wherein the monofunctional polyetheramine (B1) has a weight average molecular weight in the range from ≥ 120g/mol to ≤ 10000g/mol, as determined by GPC.

10. The copolymer according to any of embodiments 1 to 7, wherein the monofunctional polyether alcohol (B2) has the formula (B2):

wherein o and p are independently integers in the range of 0 to 2000;

wherein o + p is within the range of more than or equal to 1 and less than or equal to 4000;

q is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

11. The copolymer according to any of embodiments 1 to 10, wherein the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 150g/mol to ≤ 10000 g/mol.

12. The copolymer according to embodiment 1, wherein the intermediate product (C) obtained in step a.

13. The copolymer according to embodiment 1, wherein the at least one reactive double bond reactive component (D) is selected from the group consisting of imidazole, 1H-imidazol-1-amine, (1H-imidazol-1-yl) methylamine, (1H-imidazol-1-yl) ethan-1-amine, 3- (1H-imidazol-1-yl) propan-1-amine, 4- (1H-imidazol-1-yl) butan-1-amine, 5- (1H-imidazol-1-yl) pentan-1-amine, N-ethyl-2- (1H-imidazol-1-yl) ethan-1-amine, (1H-imidazol-1-yl) methanethiol, 2- (1H-imidazol-1-yl) ethane-1-thiol, 3- (1H-imidazol-1-yl) propane-1-thiol, 4- (1H-imidazol-1-yl) butane-1-thiol, (1H-1,2, 3-triazol-1-yl) methylamine, 1H-1,2, 3-triazole, 2- (1H-1,2, 3-triazol-1-yl) ethan-1-amine, 3- (1H-1,2, 3-triazol-1-yl) propan-1-amine, 4- (1H-1,2, 3-triazol-1-yl) butan-1-amine, and mixtures thereof, 5- (1H-1,2, 3-triazol-1-yl) pentan-1-amine, (1H-1,2, 3-triazol-1-yl) methanethiol, 2- (1H-1,2, 3-triazol-1-yl) ethane-1-thiol, 3- (1H-1,2, 3-triazol-1-yl) propane-1-thiol, 4- (1H-1,2, 3-triazol-1-yl) butane-1-thiol, 5- (1H-1,2, 3-triazol-1-yl) pentane-1-thiol, 4H-1,2, 4-triazole, (4H-1,2, 4-triazol-4-yl) methylamine, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-amine, 3- (4H-1,2, 4-triazol-4-yl) propan-1-amine, 4- (4H-1,2, 4-triazol-4-yl) butan-1-amine, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-amine, (4H-1,2, 4-triazol-4-yl) methanethiol, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-thiol, 3- (4H-1,2, 4-triazol-4-yl) propan-1-thiol, 4- (4H-1,2, 4-triazol-4-yl) butan-1-thiol, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-thiol, (1H-tetrazol-1-yl) methylamine, 2- (1H-tetrazol-1-yl) ethan-1-amine, 3- (1H-tetrazol-1-yl) propan-1-amine, 4- (1H-tetrazol-1-yl) butan-1-amine, N-methyl-4- (1H-tetrazol-1-yl) butan-1-amine, 5- (1H-tetrazol-1-yl) pentan-1-amine, (1H-tetrazol-1-yl) methanethiol, 2- (1H-tetrazol-1-yl) ethane-1-thiol, 3- (1H-tetrazol-1-yl) propane-1-thiol, 4- (1H-tetrazol-1-yl) butane-1-thiol, 5- (1H-tetrazol-1-yl) pentan-1-thiol, N, N-diethyl-1, 4-butanediamine, 1- (2-aminoethyl) piperazine, 2- (1-pyrrolidinyl) ethylamine, 4-amino-2-methoxypyrimidine, 2-dimethylaminoethanol, 1- (2-hydroxyethyl) piperazine, 4- (2-hydroxyethyl) morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N-dimethyl-1, 3-propanediamine, 4- (2-aminoethyl) pyridine, 2-amino-6-methoxybenzothiazole, 4-aminomethylpyridine, N-diallylmelamine, 3-amino-1, 2, 4-triazole, 1- (3-aminopropyl) imidazole, 1- (2-aminoethyl) imidazole, 2-hydroxy-2-methyl-benzothiazole, and the like, 4- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) imidazole, 3-mercapto-1, 2, 4-triazole, 1- (2-aminoethyl) imidazolidin-2-one, benzylamine, aniline, branched or linear (C)₂H₅N)_1-500And salts thereof.

14. The copolymer according to any of embodiments 1 to 13, wherein the copolymer has a weight average molecular weight M_wMeasured by GPC in the range of 1000g/mol or more to 100000g/mol or less.

15. A method of making a copolymer according to any of the preceding embodiments, wherein the method comprises the steps of:

i) mixing at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond with at least one isocyanate-reactive component (B) to give a mixture; ii) heating the mixture obtained in step a. to the desired temperature to obtain intermediate product (C);

16. The process according to embodiment 15, wherein step ii) is carried out at a temperature in the range from ≥ 20 ℃ to ≤ 150 ℃.

17. The method according to embodiment 15 or 16, wherein steps i) -iv) are carried out in the presence or absence of at least one solvent.

18. The method according to embodiment 17, wherein the at least one solvent is selected from the group consisting of ketones, esters, aromatic solvents, aliphatic solvents, cyclic ethers, and mixtures thereof.

19. The process according to any one of embodiments 15 to 18, wherein step iv) is carried out at a temperature in the range from ≥ 20 ℃ to ≤ 150 ℃.

20. A liquid composition in the form of a dispersion comprising a copolymer according to any one of embodiments 1 to 14 or obtained according to the process of any one of embodiments 15 to 19 and a particulate solid material selected from pigments and fillers and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent selected from an organic solvent or water or a mixture of both.

21. The liquid composition according to embodiment 20, wherein the weight ratio of the particulate solid material to the copolymer according to any one of embodiments 1 to 15 or the copolymer obtained by the process according to any one of embodiments 16 to 20 is in the range of ≥ 100:1 to ≤ 1: 50.

22. A liquid composition according to embodiment 20 or 21, comprising:

a) from ≥ 1% to ≤ 70% by weight, based on the total weight of the liquid composition, of at least one particulate solid material selected from pigments and fillers;

b) from ≥ 0.5% by weight to ≤ 50% by weight, based on the total weight of the liquid composition, of the copolymer according to any one of embodiments 1-14 or the copolymer obtained by the method according to any one of embodiments 15-19; and

c) from ≥ 10% by weight to ≤ 98.5% by weight, based on the total weight of the liquid composition, of at least one liquid diluent.

23. The liquid composition according to embodiment 22, in the form of a millbase, a coating composition or an ink.

24. Use of the copolymer according to any one of embodiments 1 to 14 or the copolymer obtained by the process according to any one of embodiments 15 to 19 and salts thereof as a dispersant for particulate solid materials selected from pigments and fillers.

Examples

The invention is further illustrated by the following examples. These examples are provided to illustrate the invention but are in no way intended to limit the scope of the invention. The chemicals listed below were used and are all commercially available. Materials:

Basonat HI

(from BASF SE) is a polyisocyanate based on isocyanurated hexamethylene diisocyanate.

Laromer PR

(from BASF SE) is a low viscosity polyisocyanate unsaturated acrylate resin based on allophanatized hexamethylene diisocyanate. It has an NCO content in the range of 14.5-15.5%.

Jeffamine

(available from Huntsman Corporation) is a blend containing 10 PO (propylene oxide) and 31 EO (ethylene oxide) having a weight average molecular weight in the range of 1500-Alkene) are used.

N- (3-aminopropyl) imidazole was purchased from BASF SE.

Molecular weights were calculated using the GPC method. The instrument used was 1260 Infinity von Agilent using polystyrene as an internal standard for calibration. The flow rate of the eluent is 1mL/min at a pressure of 70-85 bar. The column temperature was maintained at about 40 ℃.

Comparative examples 1 to 5

Mixing Jeffamine

(1 eq based on NCO) and aminopropylimidazole (0.1-0.5 eq based on NCO) were added to a 500mL reaction flask. The isocyanurate intermediate (Basonate) was added over 5 minutes

). The reaction mixture was heated to 50-60 ℃ and reacted until complete NCO consumption to give the dispersant.

Examples 6 to 13

Mixing Jeffamine

(1-1.1 eq based on NCO) was charged to a 500mL reaction flask. The allophanate intermediate (Laromer PR) is reacted in 5 minutes

) Is added to the compound. The reaction mixture was heated to 50-60 ℃ and reacted until complete NCO consumption. Aminopropylimidazole (0.25 to 0.90eq based on the double bond in Laromer) is added to the reaction mixture and heated at a temperature in the range of 75 to 85 ℃ until the aminopropylimidazole has reacted to completion to give the dispersant of the invention.

TABLE 1

The dispersants of the invention, comparative dispersants and reference products were tested on carbon blacks that were difficult to disperse in resin-free pigment concentrates.

Mill-bases were prepared by mixing pigment (Monarch 1300) and dispersant with 1-methoxy-2-propyl acetate (MPA) (total RFPC 35G, milling media 35G glass beads). The mixture was mixed for 4 hours using Skandex and the glass beads were removed by filtration. The viscosity of the resulting pigment dispersion was measured after 24 hours using a Paar Physika UD 200 rheometer with cone/plate geometry. In the range of 0.01-1024s^-1The viscosity is measured over the shear range of (a). The resulting millbase was stored at 50 ℃ for 2 weeks and the viscosity was measured again. The results are tabulated in table 2.

TABLE 2

It can be seen from the table shown above that the dispersant of the present invention provides a stable liquid composition even when stored for 2 weeks.

The reference example is prepared by reacting a polyisocyanate with a polyester (prepared from caprolactone and cetyl alcohol) and aminopropylimidazole [ this reference is based on EP0154678B2 ].

Claims

1. A copolymer obtained by:

b. reacting the intermediate product (C) obtained in step a. with at least one reactive double bond reactive component (D) to obtain said copolymer;

wherein said at leastAn isocyanate-reactive component (B) selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetherols (B2), C₆-C₃₀Monofunctional alcohols (B3) and monofunctional polyesterols (B4).

2. The copolymer according to claim 1, wherein the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond contains 1,2,3, 4, 5, 6, 7, 8, 9 or 10 NCO groups.

3. The copolymer according to claim 1, wherein the at least one isocyanate (a) comprising at least one allophanate group and at least one activated double bond is obtained by reacting at least one polyisocyanate (a1) with at least one compound of formula (a 2):

wherein Z is selected from-O-, -NR₅-and-S-;

R₁and R₂Independently of one another, from H or CH₃Substituted or unsubstituted linear or branched C₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl;

k. m and n are each independently an integer in the range of 1 to 20;

R₅selected from H, substituted or unsubstituted, linear or branchedC₁-C₃₀Alkyl, substituted or unsubstituted, linear or branched C₂-C₃₀Alkenyl and substituted or unsubstituted phenyl.

4. The copolymer according to claim 3, wherein the at least one polyisocyanate (A1) is selected from 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 3-or 1, 4-phenylene diisocyanate, triphenylmethane-4, 4',4 "-triisocyanate, polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, 1, 3-cyclobutane diisocyanate, 1, 3-or 1, 4-cyclohexane diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane, 2, 4-or 2, 6-hexahydrotoluene diisocyanate, hexahydro-1, 3-or-1, 4-phenylene diisocyanate and perhydro-2, 4 '-or-4, 4' -dicyclohexylmethane diisocyanate.

5. The copolymer according to claim 3, wherein the at least one compound of formula (A2) is selected from the group consisting of hydroxyacrylate (A2a) and hydroxyacrylamide (A2 b).

6. The copolymer according to claim 3 or 4, wherein the at least one compound of formula (A2) is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyethyl acrylamide and hydroxyethyl methacrylamide.

7. The copolymer according to any of the preceding claims, wherein the at least one isocyanate (A) has an activated double bond in the range from ≥ 1 to ≤ 10.

8. The copolymer according to any of the preceding claims, wherein the at least one activated double bond is a double bond conjugated with at least one carbonyl group.

9. The copolymer according to claim 1, wherein the monofunctional polyetheramine (B1) has the formula (B1):

o and p are each independently an integer in the range of 0 to 2000;

wherein o + p is an integer ranging from 1 to 4000; and

10. The copolymer according to claim 9, wherein the monofunctional polyetheramine (B1) has a weight-average molecular weight, determined by GPC, in the range from ≥ 120g/mol to ≤ 10000 g/mol.

11. The copolymer according to claim 1, wherein the monofunctional polyether alcohol (B2) has the formula (B2):

wherein o and p are independently integers in the range of 0 to 2000;

wherein o + p is an integer ranging from 1 to 4000;

12. The copolymer according to claim 11, wherein the monofunctional polyether alcohol (B2) has a weight-average molecular weight, determined by GPC, in the range from ≥ 150g/mol to ≤ 10000 g/mol.

13. The copolymer according to claim 1, wherein the intermediate product (C) obtained in step a.

14. The copolymer according to claim 1, wherein the at least one reactive double bond reactive component (D) is selected from the group consisting of imidazole, 1H-imidazol-1-amine, (1H-imidazol-1-yl) methylamine, (1H-imidazol-1-yl) ethan-1-amine, 3- (1H-imidazol-1-yl) propan-1-amine, 4- (1H-imidazol-1-yl) butan-1-amine, 5- (1H-imidazol-1-yl) pentan-1-amine, N-ethyl-2- (1H-imidazol-1-yl) ethan-1-amine, (1H-imidazol-1-yl) methanethiol, 2- (1H-imidazol-1-yl) ethane-1-thiol, 3- (1H-imidazol-1-yl) propane-1-thiol, 4- (1H-imidazol-1-yl) butane-1-thiol, (1H-1,2, 3-triazol-1-yl) methylamine, 1H-1,2, 3-triazole, 2- (1H-1,2, 3-triazol-1-yl) ethan-1-amine, 3- (1H-1,2, 3-triazol-1-yl) propan-1-amine, 4- (1H-1,2, 3-triazol-1-yl) butan-1-amine, and mixtures thereof, 5- (1H-1,2, 3-triazol-1-yl) pentan-1-amine, (1H-1,2, 3-triazol-1-yl) methanethiol, 2- (1H-1,2, 3-triazol-1-yl) ethane-1-thiol, 3- (1H-1,2, 3-triazol-1-yl) propane-1-thiol, 4- (1H-1,2, 3-triazol-1-yl) butane-1-thiol, 5- (1H-1,2, 3-triazol-1-yl) pentan-1-thiol, 4H-1,2, 4-triazole, (4H-1,2, 4-triazol-4-yl) methylamine, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-amine, 3- (4H-1,2, 4-triazol-4-yl) propan-1-amine, 4- (4H-1,2, 4-triazol-4-yl) butan-1-amine, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-amine, (4H-1,2, 4-triazol-4-yl) methanethiol, 2- (4H-1,2, 4-triazol-4-yl) ethan-1-thiol, 3- (4H-1,2, 4-triazol-4-yl) propan-1-thiol, 4- (4H-1,2, 4-triazol-4-yl) butan-1-thiol, 5- (4H-1,2, 4-triazol-4-yl) pentan-1-thiol, (1H-tetrazol-1-yl) methylamine, 2- (1H-tetrazol-1-yl) ethan-1-amine, 3- (1H-tetrazol-1-yl) propan-1-amine, 4- (1H-tetrazol-1-yl) butan-1-amine, N-methylbutan-1-amine-4- (1H-tetrazol-1-yl) butan-1-amine, 5- (1H-tetrazol-1-yl) pentan-1-amine, (1H-tetrazol-1-yl) methanethiol, 2- (1H-tetrazol-1-yl) ethane-1-thiol, 3- (1H-tetrazol-1-yl) propane-1-thiol, 4- (1H-tetrazol-1-yl) butane-1-thiol, 5- (1H-tetrazol-1-yl) pentane-1-thiol, N-diethyl-1, 4-butanediamine, 1- (2-aminoethyl) piperazine, N-diethyl-1, 4-butanediamine, N-dimethyl-1-pentan-ol, N-dimethyl-1-methyl-1-ol, N-dimethyl-1-ol, N-methyl-1-ol, N-1-methyl-ol, N-1-ol, N-methyl-ol, N-ethyl-1-ol, N-1-methyl-ol, N-2-ethyl-1-ol, N-1-ol, N-one or a mixture thereof, 2- (1-pyrrolidinyl) ethylamine, 4-amino-2-methoxypyrimidine, 2-dimethylaminoethanol, 1- (2-hydroxyethyl) piperazine, 4- (2-hydroxyethyl) morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N-dimethyl-1, 3-propanediamine, 4- (2-aminoethyl) pyridine, 2-amino-6-methoxybenzothiazole, 4-aminomethylpyridine, N-diallylmelamine, 3-amino-1, 2, 4-triazole, 1- (3-aminopropyl) imidazole, 4- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) imidazole, 3-mercapto-1, 2, 4-triazole, 1- (2-aminoethyl) imidazolidin-2-one, benzylamine, aniline, branched or linear (C)₂H₅N)_1-500And salts thereof.

15. The copolymer according to claim 1, wherein the copolymer has a weight average molecular weight M_wMeasured by GPC in the range of 1000g/mol or more to 100000g/mol or less.

16. A process for preparing a copolymer according to any one of the preceding claims, wherein the process comprises the steps of:

iv) heating the mixture obtained in step c. to a desired temperature to obtain the copolymer;

wherein the at least one isocyanate reactive component (B) is selected from the group consisting of monofunctional polyetheramines (B1), monofunctional polyetheramines (B1)Functional polyether alcohols (B2), C₆-C₃₀Monofunctional alcohols (B3) and monofunctional polyesterols (B4).

17. The process according to claim 16, wherein step ii) is carried out at a temperature in the range from ≥ 20 ℃ to ≤ 150 ℃.

18. The process according to claim 16 or 17, wherein steps i) -iv) are carried out in the presence or absence of at least one solvent.

19. The process according to claim 18, wherein the at least one solvent is selected from the group consisting of ketones, esters, aromatic solvents, aliphatic solvents, cyclic ethers, and mixtures thereof.

20. The process according to any one of claims 16 to 19, wherein step iv) is carried out at a temperature in the range from ≥ 20 ℃ to ≤ 150 ℃.

21. A liquid composition in the form of a dispersion comprising a copolymer according to any one of claims 1 to 15 or obtained according to the process of any one of claims 16 to 20 and a particulate solid material selected from pigments and fillers and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent selected from an organic solvent or water or a mixture of both.

22. A liquid composition according to claim 21, wherein the weight ratio of the particulate solid material to the copolymer according to any one of claims 1 to 15 or obtained by the process according to any one of claims 16 to 20 is in the range of ≥ 100:1 to ≤ 1: 50.

23. A liquid composition according to claim 21 or 22 comprising:

b) from ≥ 0.5% by weight to ≤ 50% by weight, based on the total weight of the liquid composition, of a copolymer according to any one of claims 1-15 or a copolymer obtained according to the method of any one of claims 16-20; and

24. A liquid composition according to claim 23, in the form of a millbase, a coating composition or an ink.

25. Use of a copolymer according to any one of claims 1 to 15 or obtained according to the process of any one of claims 16 to 20 and salts thereof as a dispersant for particulate solid materials selected from pigments and fillers.